Color stable washing,rinsing and cleaning composition



unve'o "LT LIN-Via sums 3,503,885 Patented Mar. 31, 1970 US. Cl. 252105 8 Claims ABSTRACT OF THE DISCLOSURE Color stable cleaning agent comprising at least one anionic and/or non-ionic surfactant, at least one organic disinfectant and at least one water-soluble reducing agent.

This invention relates to surfactant compositions. It more particularly refers to such surfactant compositions which are relatively stable with respect to color changes therein.

Liquid washing, rinsing and cleaning agents are quite well known. They generally comprise aqueous solutions of anionic or non-ionic surfactants which may or may not have the conventional additive substances admixed therewith. These agents are generally used for the washing of textiles or for the cleaning of surfaces of other solid materials, such as surfaces of glasses or ceramic materials, plastics, varnished and polished surfaces which may also be of a metallic nature. One preferred field of used is the rinsing of dishes and other implements used in the kitchen. Insofar as these cleaning processes are effected by hand, they are effected at slightly elevated temperatures at which injurious microorganisms and particularly pathogenic germs are not effected. It has, therefore, been proposed to add ordinary bacteriocides to these liquid washing and cleaning agents.

It has been observed that liquid preparations containing anionic and/ or non-ionic surface-active agents and disinfectants often discolor, particularly where there has been a relatively long shelf time.

It is an object of this invention to provide means for rendering liquid surfactant composition stable against discoloration.

It is another object of this invention to provide a novel surfactant composition.

It is a further object of this invention to provide a novel washing, rinsing and cleaning composition.

Other and additional objects of this invention will become apparent from a consideration of this entire specification including the claims appended hereto.

In accord with and fulfilling these objects, one aspect of this invention includes a surfactant composition comprising at least one anionic and/or non-ionic surfactant, at least one organic disinfectant, and at least one watersoluble reducing agent. In addition to these constituents, there may be incorporated in the composition of this invention any one or more of the conventional ingredients used in the surfactant industry. The composition medium may be water.

It is suitable in the practice of this invention to utilize the surfactant in a proportion of about to 40 weight percent, the organic disinfectant in a proportion of about 0.1 to 5 weight percent and the reducing agent in a proportion of about 0.01 to 5 weight percent, each based upon the total amount of surfactant and disinfectant utilized.

It is not known just why the incorporation of a reducing agent should affect the color stability of surfactant compositions according to this invention. It may be pos tulated, Without being in any way bound thereby, that the reducing agent in some way interacts with either the surfactant or the disinfectant, or both, portion of the composition so as to render the interaction product more resistant to discoloration than is the surfactant and disinfectant combination alone.

As noted above, the surfactant may be non-ionic or anionic in character. Anionic surfactants are in general within the scope of this invention. Illustrative of the types of anionic surfactants included herein, are those having at least one hydrophobic group of about 8 to 24 carbon atoms, generally in an aliphatic or alicyclic configuration. It is within the spirit and scope of this invention to utilize either saturated or unsaturated hydrophobic groups, e.g. octyl, octenyl, dodecyl, oleyl, stearyl, cyclodecenyl, linolenyl, nonadecyl, cyclododecatrienyl, palmityl, cyclooctyl cyclohexyl-decyl, etc. The hydrophobic group is suitably joined to an anionic water-solubilizing group, either directly or via an intermediate or bridging group. Where a bridging group is used, it may for example be a benzene ring, a carboxylic acid ester, a carbon amide or an alkylene glycol group, e.g. ethylene or propylene glycol.

As anionic wash-active substances, there can be used soaps derived from natural or synthetic fatty acids, and possibly also from resin and naphthenic acids. Among the best known synthetic anionic surfactants are the sulfonates, for instance the alkylaryl sulfonates and particularly alkyl benzene sulfonates having about 9-15 carbon atoms in the alkyl radical. There are primarily of interest aliphatic surfactants such as can be formed from preferably saturated hydrocarbons containing about 9 to 15 carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine, or sulfoxidation with sulfur dioxide and oxygen and conversion of the resultant intermediate products into the sulfonates in the conventional manner. In the sulfonates prepared in this manner, the sulfonate group is usually on a secondary carbon atom; however, there can also be used aliphatic sulfonates obtained by known methods whose sulfonate group is on a primary carbon atom. As aliphatic sulfonates there can, furthermore, be employed products which can be obtained by sulfonation with sulfur trioxide of terminal or non-terminal C C olefins. The sulfonates which are to be used in accordance with the invention also include the esters of an a-sulfo fatty acids with monohydric or polyhydric alcohols containing 1 to 4 and preferably 1 to 2 carbon atoms.

As anionic surfactants of the sulfate type, there may be mentioned fatty alcohol sulfates, sulfated fatty acid alkylolamides, sulfated fatty acid monoglycerides and the sulfonation products of ethoxylated and/or propoxylated fatty alcohols, alkyl phenols having about 8 to 15 carbon atoms in the alkyl radical, fatty acid amides, fatty acid alkylolamides, etc., about 1 to 8, and preferably about 2 to 4, glycol ether groups being possibly present in a molecule. Sulfonation products of the sulfate type which can be used in the invention can also be prepared from terminal or non-terminal C -C olefins.

As non-ionic surfactants, there are preferred the addition products of alkyleneoxide, e.g. ethylene oxide, propylene oxide and/or the addition products of ethylene oxide and propylene oxide, to fatty alcohols, fatty acids, alkyl phenols, fatty acid amides, fatty acid alkylolamides and similar compounds having at least one reactive hydrogen atom. The number of glycol units present in the molecule can vary between about 4 and 20, and preferably about 5 and 15, and should be sufficient to impart to the products cloud points of at least about 20 C. Amine oxides are also included here among the non-ionic surfactants.

The foaming power of the prepartions of the invention can be increased or reduced by suitable combinations of different wash-active substances. When desired, foam stabilizers or foam inhibitors can also be added. In gen= eral, importance is placed on good foaming power in the case of hand dishwashing agents used in the household; in the case of dishwashing agents for commercial or industrial purposes, or for dishwashing machines including those used in the household, a low production of foam is generally desired As foam stabilizers there are particularly suited the well-known fatty acid alkylolamides and particularly the fatty acid monoethanol amides. As foam inhibitors, there can be used inter-alia addition products of propylene oxide to the non-ionic polyethylene glycol ethers described above.

Insofar as the anionic or non-ionic surfactants are derived from fatty acids or fatty alcohols, they can preferably contain 12 to 14 carbon atoms per fatty acid or fatty alcohol radical.

The disinfectants which can be used in acordance with the invention include preferably the halogenated phenol, the halogenated diaryl or cycloalkyl urea and the halogenated N-aryl-, or cycloalkyl saliscylylamide types; however, these compounds should not have any oxidizing properties, i.e. the halogen atoms are to be bound to carbon. Aryl groups may be exemplified by phenyl, xylyl, biphenyl, naphthyl, etc. Cycloalkyl groups may be exemplified by cyclohexyl, cyclopentyl, cyclooctyl, methyl cyclohexyl, etc.

The halogenated phenol types include, for instance, chlorination and bromination products of phenol such as pentachlorophenol, and furthermore halogenated cresols, xylenols such as for instance 4-bromo-3,5-xylenol, or halogenated cyclohexyl-, methylcyclohexyl or benzyl phenols; chlorobenzyl phenol; bis(halo hydroxy phenyl)- alkylene; bis(halo hydroxy phenyl)-sulfide; bis(halo hydroxy phenyl)-alkylidene; halophenyl urea; and N-halo phenyl-halo-hydroxy phenyl formamide. Instances of halophenol ureas include 4,3',4-trichloro-N,N-diphenyl urea and 3,3,4-trichloro-N,N-diphenyl urea.

Compounds of the halogenated bisphenol type can also be {.lSfid. They can, for instance, have the following formu a:

HO OH lXin Yn in which X and Y are halogen atoms such as chlorine or bromine, m and n are whole numbers from 1 to 3 and R is a bivalent radical such as sulfur, or alkylene or alkylidene radicals containing about 1 to 4 carbon atoms. The halo genated bisphenols which can. be used in accordance with the invention include for instance, bis-(2-hydroxy-3,5,6- tric'hlorophenyl)-methane, bis-(2 hydroxy-3,5-dichlorophenyl)-methane, bis-(Z-hydroxy 4,5 dich1orophenyl)- methane, bis-(2 hydroxy)-3,4-dichlorophenyl)-methane, bis-(2-=hydroxy-5-chlorophenyl)-methane, bis(2 hydroxy- 5-bromophenyl)-methane, bis(2-hydroxy 3,5 dichlorophenyl)-sulfide, bis(Z-hydroxy 5 chlorophenyl)-sulfide, etc.

Furthermore, the bactericides (disinfectants) to be used in accordance with the invention include halogenated carbanilides of the general formula:

N 1-1-0 0 NH--R of R can be taken, for instance, by the following radicals: 2-chlorophenyl-, 3-chlorophenyl, 4-chlorophenyl-, 3- brornophenyl-, 4-bromophenyl-, 2,4-dichlorophenyl, 2,3 dichlorophenyl-, 3,4,5 trichlorophenyl-, 3,4,5 tribromophenyl-, 3 chloro 4 methylphenyl, 4 chloro 3-methylphenyl-, 4-chlor-2-methylphenyl, 2,5-dichloro-4- methylphenyl-, 4-chloro-3,5-dimethylphenyl-, 4-chloro-4- ethylphenyl, 3-chloro-4-isopropylphenyl-, 3-chloro-4-n butyl-phenyl-, 3 chloro 4 tert.-butylphenyl-, chlorobiphenyl, etc. There are preferably used 3,34'- trichlorocarbanilide or 4,33'-trichlorocarbanilide or compounds in which the chlorine atoms are replaced in whole or in part by bromine atoms.

Finally, there enters into consideration as disinfect= ants halogenated salicylanilides of the formula:

in, which R, is hydrogen, chlorine or bromine, X or X are hydrogen, chlorine, bromine, iodine and/or CH X is hydrogen, chlorine, bromine, or trifiuoromethyl and X is hydrogen, chlorine or bromine, at least three f the X substituents being halogen atoms. In accordance with the invention, there can be used, for instance, 5-chlo rosalicylyl 3,4 dichloranilide, 4,5-dichlorosalicylyl-3,4 dichloranilide, 4,5-dichlorosalicylyl-2,3-dichloranilide, 5=- chlorosalicylyl-23'4-trichloranilide, 5-chlorosalicylyl-2,3, 4-trichloranilide and 3,5-dichlorosalicylyl-2,3,4-trichloran= ilide. In the said illustrative compounds, the chlorine atoms can be replaced in while or in part by bromine atoms such as, for instance, 4,S-dibromosalicylanihde and in 3,4,5-tribromosalicylanilide.

In many cases it is possible, by combination of ditfer= ent disinfectants, to obtain special effects. The disinfectants to be combined can belong to the same type; how ever, members of different of the above-mentioned types of disinfectants can also be incorporated jointly into the products in accordance with the invention. Thus, for instance, a mixture of approximately equal parts of 4',5- dibromosalicylanilide and 3,4S-tribromosalicylanilide has proven useful.

As water-soluble reducing agents to be used in accord" ance with the invention, there enter into consideration water-soluble inorganic reductive nitrogen compounds such as salts of hydrazine or hydroxylamine, for examp e, hydrazinium sulfate or hydroxyl ammonium chloride, or water-soluble salts of reductive acids of sulfur or of P1108= phorus, e.g. sodium dithionite, sodium sulfite, sodium pyrosulfite, sodium thiosulfate, sodium hypophosphite and sodium hydroxymethane sulfinate. These reducing agents, of which the salts of reductive acids of sulfur have the greatest practical importance, are preferably used in quantities of 0.1 to 2.5% by weight, referred to the anhy= drous components of the preparation.

In addition to the surfactants and the bactericidal sub stances there can also be present other addition substances which either improve the homogeneity of the preparations or make them more suitable for special purposes of use, for instance as textile washing agents.

In order to improve the homogeneity of the combination compositions of this invention, hydrotropic substances and/or sedimentation stabilizers may be added thereto. As hydrotropic substances, water-soluble organic solvents having boiling points of at least 70 C., such as the aliphatic mono-alcohols having about 2 to 4 carbon atoms as well as ether alcohols having about 3 to 10 car bon atoms, for instance the mono-ethers of mono-, di or triethylene glycol with methyl, ethyl, propyl or butyl alcohols, as well as water-soluble partial ethers of said monohydric alcohols with glycerin, di-glyoerin or tri-glycerin, etc. have been found to be useful. There can also be used lower aromatic sulfonates such as benzene, to u ene, xylene or naphthalene sulfonate. Urea can also be used as hydrotropic substance.

Stability upon storage and, in particular, sedimentation stability, can be obtained where required by incorporating water-soluble thickening agents. These include, for instance, salts of polyacrylic acid or polyrnethacrylic acid.

The compositions of this invention can also contain phosphates such as pyroand tripolyphosphates. These phosphates can be replaced in whole or in part by other coingexing agents, such as the salts of nitrilotriacetic acid or e ylene diaminotetra-acetic acid. The quantity of these phosphates and/ or complexing agents depends on the field of use; cleaning agents for surfaces of solid materia s, particularly for dishwashing agents, frequently contain only such quantities of phosphates and/or other complexing agents as dissolve in the aqueous phase. In the case of fine washing agents or other textile washing agents on the other hand, it is advisable to incorporate larger quantities of phosphates and/or other complexing agehts which are then to be sure suspended as undissolved components.

If the products in accordance with the invention are to be used, in particular, in the household as fine wash= ing" agents or hand dishwashing agents, it may be advisable to incorporate skin-protecting and/r skin oil re= plenishing substances. As skin-protecting surfactants there are recommended, in addition to the indicated nononics, the'sulfation products of non-ionics and, in particular, the sulfated addition products of about 1 to 20, and preferably about 6 to 18, mols of ethylene oxide to fatty alcohols. As skin oil replenishing, skin-protective agents, there enter into consideration fatty alcohols as well as other water-insoluble fatty substances which contain hydroxyl groups such as, for instance, fatty acid mono-glycerides, fatty acid monoethylene glycol esters, etc. These substances are present in dispersed condition in the liquid washing agents and thus cause such compositions to appear to be cloudy. If desired, one can also of course incorporate other clouding agents such as polystyrene dispersions.

In so far as the products in accordance with the inventiop are to be used for the treatment of textiles, they can also contain the known optical brighteners.

Frequently the liquid washing agents present on the market are differently colored, for instance red, orange, yellow, green, blue or violet. These colors may be very soft pastel shades or stronger colors as desired. Specifically in 'the case of such colored liquid washing agents, the changes in color by the action of sun make themselves unpleasantly perceptible. These discolorations can be observed both in the case of glass, or plastic containers. Such discoloration is particularly noticeable with uncolored glass or plastic or with transparent containers. Colored containers make the discoloration less apparent but do not prevent the composition from discoloring.

The preparations in accordance with the invention are in the form of aqueous solutions which contain:

About to 40% by Weight and preferably about to 35% by weight of anionic and/or non-ionic surfactants;

About 0.1 to 5% by weight and preferably about 0.1 to

2% by weight of disinfectants;

About 0.01 to 5% by weight and preferably about 0.1

to 2.5% by weight of reduction agents;

each based upon the mixture of surfacants and bactericides. In addition to this, there may also be present the following materials:

Up to about 20% by weight and preferably about 10 to by weight of solubilizers;

Up to about 35% by weight and preferably up to about 15 by weight of water-soluble anhydrous phosphates and/or other complexing agents;

Up to about 3% by weight and preferably up to about 0.5% by weight 0t clouding agents, such as polystyrene, ethylene glycol distearate, etc.

In addition, smaller quantities of buffer substances, fragrances, preservatives, coloring substances, etc. can be incorporated.

The following examples are given by way of illustration-of this invention and are in no way restrictive upon the scope hereof. Components of the compositions of these examples which are capable of existing in salt form are present as sodium salts but named as the compound without reference to the salt.

EXAMPLE 1 An aqeuous solution of the following composition was prepared:

Percent by weight Dodecylbenzene sulfonate 0 Lauryl diethylene glycol ether sulfate 5 Urea 5 Ethylene glycol monoethyl ether 10 Benzoate 0.2 Perfume 0.1 Trichlorocarba'nilide 0.2 Water Balance This composition was light yellow in color. This solution was left for 3 to 4 weeks during the sunny time of the year in a clear colorless glass bottle on a window facing the south, i.e. under the action of sunlight, whereupon it turned a yellowish brown color. This same composition containing in addition 0.1% by weight dithionite remained substantially unchanged in color under the same conditions of storage.

EXAMPLE 2 An aqueous solution wasp repared consisting of:

Percent by weight Lauryl sulfate 5 Myristyl sulfate 5 Addition product of 8 mols of ethylene oxide to 1 mol of fatty acid mono ethanolamine (14 to 20 carbon atoms in the fatty acid radical) 8 Red dyestuff (commercial product: Rhodamin B)- 0.0004 Isopropanol l0 Perfume 0.05 p-Chloro-m-cresol 2 Water Balance This composition had a red color upon preparation. Upon standing under the conditions indicated in Example 1, the color changed into a dirty gray. Addition of 0.5% by weight of s'jiilfite to the composition at the time of its preparation caused the color to remain unchanged under the storage conditions indicated.

EXAMPLE 3 An aqueous solution was prepared consisting of:

Percent by weight Dodecyl benzene sulfonate 20 Sulfonated addition product of 4 mol ethylene oxide This composition was a goldish-yellow color immediately after preparation. When the solution was stored under the conditions indicated in Example 1, the color 7 changed into a dirty gray, which color change was prevented by addition of 0.05% by weight hydroxymethane sulfonate before the storage,

EXAMPLE 4 A fine washing agent present as suspensionwith pearl luster of the following composition was prepared:

Percent Ethanolamine salt of an oz-SlllfO fatty acid ethylester with 12 to 18 carbon atoms in the fatty acid radi- This composition had a brownish-yellow color immediately after its preparation. When this solution was stored under the conditions indicated in Example 1, the color changed into a disagreeable grayish-brown. This color change was prevented by the addition of 0.2% hydroxylamine hydrochloride,

The disinfectants present in the dishwashing agents in accordance with the invention show their action not only in the washing solution and on materials washed, particularly' dishes, but also on the dishcloths used for the washing. Since these dishcloths frequently lie moist after the washing, they develop a musty odor which in all probability is due to the development of microorganisms. With use of the washing agents in accordance with the invention, this undesired development of odor is avoided.

What is claimed is:

1, A composition consisting essentially of about to 40 weight-percent of at least one surfactant selected from the group consisting of natural and synthetic anionic and synthetic non-ionic surfactants, about 0.1 to 5 weightpercent of at least one halogenated organic disinfectant selected from the group consisting of halogenated phenols, halogenated bisphenols, halogenated diarylureas, halogenated N-aryl-salicylamides, halogenated carbanilides and halogenated salicylanilides and about 0.01 to 5 weightpercent of at least one water soluble inorganic reducing agent selected from the group consisting of hydrazine sulfate, hydroxylamine hydrochloride, sodium dithionite. sodium sulfite, sodium pyrosulfite, sodium thiosulfate, sodium hypophosphite and sodium hydroxymethanesulfinatc. wherein each of said quantities is based upon the total weight of surfactant and disinfectant.

2, A composition according to claim 1 wherein said surfactant is present in an amount of about to 35 weight-percent; said disinfectant is present in an amount of about 0.1 to 2 weight-percent; and said reducing agent is present in an amount of about 0.1 to 2.5 weight-percent; wherein each of said quantities is based upon the total weight of surfactant and disinfectant.

3, A composition according to claim 1 wherein said disinfectant is at least one selected from the group consisting of 4-bromo-3,5-xylenol; bis-(2-hydroxy- 3,5,6-trichlorophenyl)-methane; bis-(2-hydroxy-4,S-dichlorophenyl)-methane; bis-(2-hydroxy-3,4-dichlorophenyl) methane; bis-(2-hydroxy-5-chlorophenyl)-methane; bis-(2-hydroxy-S-bromophenyl)-methane; bis (2-hydroxy-3,5-dichlorophenyl)-sulfide; bi (2-hydroxy-5-chlorophenyl)- sulfide; 2-chlorophenyl dichloro carbanilide; 3-chlorophenyl dichloro carbanilide; 4 bromophenyl dichloro carbanilide; 2,4-dichlorophenyl-dichloro carbanilide; 2,3- dichlorophenyl-dichloro carbanilide; 3,4-dichloro phenyldichloro carbanilide; 3,4,S-trichlorophenyl-dichloro carbanilide; 3,4,5-tribrornophenyl-dichloro carbanilide; 3-chloro-4-methyl phenyl-dichloro carbanilide; 4-chloro-3-meth=- ylphenyl-dichloro carbanilide; 4-chloro-2-methyl phenyldichloro carbanilide; 2,5-dichloro-4-methyl phenyl-dichlor0 carbanilide; 4-chloro-3,5-dimethyl phenyl-dichloro carbanilide; 4-chloro 4 ethyl phenyl-dichloro carbanilide; 3-chloro-4-isopropyl phenyl-dichloro carbanilide; 3-chloTo- 4-n-buty1 phenyl-dichloro carbanilide; 3-chloro 4 tert. butyl phenyl-dichloro carbanilide; 3-chloro-biphenyl dichloro carbanilide; 3,3,4-trichloro-N,N-diphenyl urea; 4,3'4-trichloro-N,N-diphenyl urea; 5-chloro salicylyl-3,4- dichloro anilide; 4,5 dichloro salicylyl 3,4 dichloro anilide; 4,5-dichloro salicylyl 2,3 dichloroanilide; 5-chlo'rosalicylyl-2,3,4-trichloroanilide; 3,5-dichloro salicylyl-2,3,4- trichloro anilide; 4',5-dibromo salicylanilide; and 3,4,5- tribromo salicylanilide,

4. A composition according to claim 1 wherein said composition additionally contains up to about 20 weightpercent of a water-soluble organic solvent, up to 35 weight-percent of at least one complexing agent selected from the group consisting of water soluble anhydous'phosphate and up to about 3 weight-percent of at least one clouding agent selected from the group consisting of polystyrene and ethylene glycol distearate.

5. A composition according to claim 1 consisting essentially of:

Percent by weight Sodium dodecylbenzene sulfonate 2O Lauryl diethylene glycol ether sulfate 5 Urea 5 Ethylene glycol monoethyl ether 10 Sodium benzoate 0.2

Perfume 0.1 Trichlorocarbanilide 0.2

Water Balance 6. A composition according to claim 1 consisting essentially of;

Percent by weight Lauryl sulfate 5 Myristyl sulfate 5 Addition product of 8 mols of ethylene oxide to 1 mol of fatty acid mono-ethanolamine (14 to 20 carbon atoms in the fatty acid radical) 8 Red dyestuif 0.0004 Isopropanol l0 Perfume 0.05 p-Chloro-m-cresol 2 Water Balance 7, A composition according to claim 1 consisting essentially of Percent by weight Sodium dodecyl benzene sulfonate 20 Sulfonated addition product of 4 mol ethylene oxide and 1 mol of a C C fatty alcohol mixture 12 Addition product of 10 mols ethylene oxide to 1 mol nonylphenol 8 Xylene sulfonate 4 Polystyrene 0.1 Ethanol 5 Yellow dyestuff 0.002 Tribromosalicylanilide 0.2 Dibromosalicylanilide 0.2 Water Balance 8. A composition according to claim 1 consisting essentially of Percent Ethanolamine salt of an a-sulfo fatty acid ethylester with 12 to 18 carbon atoms in the fatty acid radical 5 Coconut fatty acid diethanolamide 5 Ethylene glycol distearate 1 Ethylene diamine tetra-acetate 1 O-phenyl phenol 0.8 Urea 5 Potassium pyrophosphate 10 Water Balance (References on following page) 9 10 References Cited 3,326,808 6/1967 Noseworthy 252-406 3,346,503 10/1967 Huggins 252106 UNITED STATES PATENTS Stecker 252106 MAYER WEINBLATT, Primary Examiner Doerr 8108 Casely et a1, 252106 XR Guest et a1 252106 XR UNITED STATES PATENT OFFICE 5 69 CERTIFICATE I OF CORRECTION Patent No. 3 503 885 Dated March 31 970 Inventor(s) HANS WEDELL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[ Column 1, line 32, "used" (first occurrence) should be I --use--; column 3, line 58, delete the closing parenthesis after "hydroxy"; colurm l, line 4, after "dichlorophenyl" insert --3,4-dichlorophenyl-, column 4, line 6, "4-chlor-2- methylphenyl," should be --4-chloro-2-methylphenyl,-column 4, line 33, "while" should be --whole-- SIGNFT $551; 5 W1 F15] sea-1970 SEAL) f Anew Edward M. Fletcher, It. WILL E. W m Atmfing officer Gomisaioner of Patents 

